WO2011126684A2 - Revêtement anticorrosion contenant de l'argent pour une protection accrue contre la corrosion et l'activité microbienne - Google Patents

Revêtement anticorrosion contenant de l'argent pour une protection accrue contre la corrosion et l'activité microbienne Download PDF

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WO2011126684A2
WO2011126684A2 PCT/US2011/028503 US2011028503W WO2011126684A2 WO 2011126684 A2 WO2011126684 A2 WO 2011126684A2 US 2011028503 W US2011028503 W US 2011028503W WO 2011126684 A2 WO2011126684 A2 WO 2011126684A2
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silver
salts
polyelectrolyte
acid
substrate
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PCT/US2011/028503
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English (en)
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WO2011126684A3 (fr
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Zhiqiang Song
Ted Deisenorth
Richard Thomas
Jacqueline Lau
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Base Se
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Publication of WO2011126684A3 publication Critical patent/WO2011126684A3/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B05D7/16—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using synthetic lacquers or varnishes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4473—Mixture of polymers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31692—Next to addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31692—Next to addition polymer from unsaturated monomers
    • Y10T428/31699—Ester, halide or nitrile of addition polymer

Definitions

  • antimicrobial metals preferably salts of antimicrobial metals, such as silver salts
  • anti-corrosive coatings surprisingly improves the protection of metals, such as those found in metallic medical devices and implants, against corrosion and substrate metal ion release while generating a multifunctional coating which also provides protection against , micro-organisms and bio-fouling.
  • Metal corrosion is a serious problem in industries as varied as automotive manufacturing and the production of medical devices and implants, as it affects and eventually destroys integrity of metal structures.
  • tissue reactions ranging from a mild response such as discoloration of surrounding tissue to a severe one resulting in pain and even loosening the implant.
  • OCP open circuit potential
  • E cor corrosion potential
  • the potential of metallic biomaterial can range from -1 to 1.2 V vs. SCE in the human body.
  • the high potential in the human body can cause localized pitting corrosion and crevice corrosion even for well known corrosion resistant metal alloys such type 316L stainless steels (SS316L) which show a pitting breakdown potential ranging from 0.4 to 0.8 V vs. SCE.
  • SS316L stainless steels
  • Polyelectrolyte coatings are known to improve corrosion resistance.
  • US Pub Pat Application No. 2004/0265603A1 discloses an anticorrosion polyelectrolyte multilayer (PEM) coating comprising a polyelectrolyte complex of two oppositely charged polyelectrolytes.
  • the polyelectrolytes are poly(diallyldimethylammonium chloride) and poly(styrene sulfonate) (PSS).
  • Silver salts such as those of nitrate, proteins, acetate, lactate and citrate have been used in anti-microbial coatings for medical devices. Silver salts are known to have better anti-microbial efficacy than silver metal due to the instant ionization/dissociation to produce the Ag + ion. The soluble salts are effective but do not provide long term protection and typically require frequent reapplication which is not always practical especially for medical implants. Attempts have been made to slow release of silver ions with silver containing complexes such as colloidal silver protein as disclosed in US Pat 2,785,153. US Pat 5,985,308 discloses a process for producing anti-microbial effect with complex silver ions for sustained silver ion release.
  • a coating containing select polymer binders and an antimicrobial metal can exhibit significantly improve anticorrosion properties while maintaining an antimicrobial sustained release of silver metal or ions.
  • the polymer binders may be those which are somewhat effective as anticorrosion coatings on their own, but the incorporation of the antimicrobial metal, such as a silver salt, greatly enhances the anticorrosion
  • the incorporation of the antimicrobial metal offers the possibility of thinner coatings or less coating layers because of the improved corrosion properties of the combination of the binder polymer with the antimicrobial metal.
  • a coated metal substrate a method of protecting a metal substrate, a kit of parts and use of an antimicrobial metal to improve corrosion resistance of the coated metal substrate.
  • the polymer binder comprises polymers selected from the group consisting of polyelectrolytes containing charged and/or potentially chargeable groups, preferably the polyelectrolytes comprise a polyelectrolyte complex derived from a positively-charged (cationic) polyelectrolyte and a negatively charge (anionic) polyelectrolyte, and polymers containing hydrophilic entities, preferably the polymer containing hydrophilic entities forms a water-insoluble film, and most preferably the polymer containing hydrophilic entities includes copolymers of styrene and vinylpyridine, homopolymers and copolymers of vinylpyridine, homopolymers and copolymers of terbutylaminoethyl methacrylate, wherein the antimicrobial metal is selected from the group of metals consisting of silver, copper, gold, iridium, palladium and platinum, preferably the antimicrobial metal is an antimicrobial metal salt or ion thereof, most
  • an antimicrobial metal preferably a antimicrobial metal salt and optionally phytic acid or salts thereof,
  • the polymer binder comprises polymers selected from polyelectrolytes containing charged and/or potentially chargeable groups, preferably the polyelectrolytes comprise a complex derived from a positively-charged (cationic) polyelectrolyte and a negatively charge (anionic) polyelectrolyte, and polymers containing hydrophilic entities, preferably the polymer containing hydrophilic entities forms a water-insoluble film, and most preferably the polymer containing hydrophilic entities includes copolymers of styrene and vinylpyridine, homopolymers and copolymers of vinylpyridine, homopolymers and copolymers of terbutylaminoethyl methacrylate, and the antimicrobial metal is selected from silver, copper, gold, iridium, palladium or platinum, preferably a salt or ion thereof and most preferably is a silver salt selected from the group consisting of silver nitrate, silver citrate, silver acetate, silver fluoride, silver permangan
  • a corrosion resistant metal substrate comprising a first part (A) comprising an anionic polyelectrolyte containing negatively charged groups and a second part (B) comprising a cationic polyelectrolyte containing positively charged groups
  • a third part (C) comprising a polymer containing hydrophilic entities, preferably the polymers containing hydrophilic entities form water-insoluble film,
  • a forth part (D) comprising an antimicrobial metal, preferably antimicrobial salt, and
  • a fifth part (E) comprising phytic acid or salts thereof, which parts (A), (B), ( D) and optionally (E) or parts (C), (D) and optionally (E) when applied to the metal substrate form a coated metal substrate as described above.
  • an antimicrobial metal preferably selected from the group consisting of salts of silver, copper, gold, iridium, palladium or platinum, to improve the corrosion resistance of a metal coating, preferably wherein the coating is on at least a part of a medical device or implant.
  • the metal substrate includes any materials which have a tendency to corrode.
  • the metals selected from the groups I A, IIA, IIIA, IVA, VA, VIA, 1MB, IVB, VB, VIB, VIIB, VIII B, IB, MB, of the periodic table.
  • Metal includes alloys.
  • Typical metal substrates may be selected from the group consisting of iron, aluminum, magnesium, copper, titanium, beryllium, silicon, chromium, manganese, cobalt, nickel, palladium, lead, cerium, cadmium, molybdenum, hafnium, antimony, tungsten, tantalum, vanadium, mixtures and alloys thereof.
  • the metal substrate is steel, aluminum, titanium, chromium, cobalt mixtures or alloys thereof.
  • the metal substrate is a steel alloy such as stainless steel (316L), aluminum, titanium, titanium alloy or chromium-cobalt alloy.
  • the metal substrate may be any shape or form.
  • the substrate includes not only planar surfaces but three-dimensional substrates.
  • the substrate may be a flake, tube, pipe or metal parts.
  • the metal substrate is at least a part of a medial device or implant.
  • Polyelectrolyte Polyelectrolytes are known to be polymeric or macromolecules containing substantial portions of repeat units which are charged or potentially charged.
  • the polyelectrolytes may be either natural (protein, starches, celluloses, polypeptides) or synthetically derived polymers.
  • the natural polymers may be modified natural polymers such as cationically modified starch or cationically modified cellulose.
  • polyelectrolytes bear a plurality of charged units arranged in a spatially regular or irregular manner.
  • the charged units may be either anionic or cationic.
  • a positively charged (or chargeable) polyelectrolyte is called a cationic polyelectrolyte, cationic polymer, polycation or polybase.
  • a negatively charged (or chargeable) polyelectrolyte is called an anionic polyelectrolyte, anionic polymer, polyanion or polyacid.
  • a polyelectrolyte carrying both positively charged groups and negatively charged groups is referred to as amphoteric polyelectrolyte or polymer.
  • Polyelectrolytes can be strong or weak depending on the dissociation ability of the electrolyte groups they bear.
  • a strong polyelectrolyte is one which dissociates completely in solution giving a charge density independent of pH (or for most reasonable pH values).
  • a weak polyelectrolyte is not fully charged but dissociates partially in solution only at certain pH range. The charge density of a weak polyelectrolyte
  • polyelectrolyte in solution is therefore pH dependent.
  • Strong polyelectrolytes contain strong acid and/or base moieties such as sulfate and sulfonate groups in anionic polyelectrolytes or quaternary ammonium groups in cationic polyelectrolytes.
  • Weak polyelectrolytes contain weak acid and/or base moieties such as carboxylic acid and/or amino groups which become charged only at high (for acid) or low (for amino) pH.
  • Natural polymers include naturally occurring polyelectrolytes (such as proteins and polynucleic acids) and synthetically modified natural polyelectrolytes (such as modified celluloses, starches or modified starches and polypeptides or modified polypeptides).
  • the binder polymer of the invention preferably contains a complex formed from a positively-charged (cationic) polyelectrolyte (B) and a negatively charged (anionic) polyelectrolyte (A).
  • the positively-charged (cationic) polyelectrolyte and the negatively charged (anionic) polyelectrolyte are each by themselves water-soluble. However, when they come in contact with one another, they complex via electrostatic interaction and/or hydrogen bonding interactions and the complex becomes water insoluble.
  • polyelectrolytes can be conveniently applied as a coating by a simple method of layer-by-layer deposition in sequence of a cationic polymer (B) and an anionic polymer(A) in aqueous solutions to form a polyelectrolyte multilayer (PEM) film on the metal substrate.
  • a cationic polymer B
  • an anionic polymer(A) in aqueous solutions to form a polyelectrolyte multilayer (PEM) film on the metal substrate.
  • PEM polyelectrolyte multilayer
  • Polyelectrolytes can be described in terms of charge density (meg/g) for both anionic and cationic polyelectrolyes.
  • the polyelectrolytes (A) and (B) each have a total charge density (q) of from 0.5 to 60 meq/g, more preferably from 1.0 to 40 meq/g, most preferably from 2 to 30, and especially from 3.0 to 20.
  • the total charge density includes contribution from any charged groups as well as potentially chargeable groups of weak electrolyte groups which become charged depending on pH.
  • the molecular weight of the synthetic or natural polyelectrolyte (A) or (B) is typically 1 ,000 to 10,000,000 Daltons, preferably 100,000 to 3,000,000, most preferably 5,000 to 1 ,000,000.
  • the molecular weight specified is preferably weight average molecular weight (M w ) which can be determined by a typical light scattering method or a GPC (gel permeation chromatography) method.
  • the polyelectrolyte anionic polymers (A) can be natural, modified natural polymers or synthetic polymers.
  • natural and modified natural anionic polymers are alginic acid (or salts), carboxymethylcellulose, dextran sulfate or poly(galacturonic acid) or salts thereof.
  • Useful synthetic anionic polymers include polymers obtained from
  • anionic monomers (l a ) include, but are not limited to, (meth)acrylic acid (or salts), maleic acid (or anhydride), styrene sulfonic acid (or salts), vinyl sulfonic acid (or salts), allyl sulfonic acid (or salts), acrylamidopropyl sulfonic acid (or salts), and the like, wherein the salts of the said carboxylic acid and sulfonic acids are preferably neutralized with an ammonium cation or a metal cation selected from the group consisting Groups IA, 11 A, IB and MB of the Periodic Table of Elements.
  • Preferred cations of the polyelectrolyte anionic polymer are ammonium cations (NH 4 + ) and + N(CH 3 ) 4 and most preferred metal cations are K + and Na + .
  • Suitable water-soluble anionic polymers are reaction products of 0.1 to 100 weight percent, preferably 10 to 100 weight percent, most preferably 50 to 100 weight percent, of at least one anionic monomer l a , and optionally 0 to 99.9 weight percent, preferably 0 to 90 weight percent, most preferably 0 to 50 weight percent, of one or more other copolymerizable monomers (II), and optionally, 0 to 10 weight percent of a crosslinking agent (III).
  • the preferred polyelectrolyte anionic natural polymers are alginate,
  • carboxymethylcellulose dextran sulfate or poly(galacturonic acid).
  • the preferred combined synthetic and natural polyelectrolyte anionic polymers (A) are homopolymers or copolymers of (meth)acrylic acid , maleic acid (or anhydride), styrene sulfonic acid , vinyl sulfonic acid , allyl sulfonic acid, acrylamidopropyl sulfonic acid, alginic acid, carboxymethylcellulose, dextran sulfate or poly(galacturonic acid) or salts thereof.
  • anionic polyelectrolytes are polystyrenesulfonate (PSS), poly(styrenesulfonate-co-maleic acid), alginic acid, carboxymethylcellulose, dextran sulfate, poly(galacturonic acid ) or salts thereof.
  • the cationic polymers can be natural, modified natural polymers or synthetic polymers.
  • natural and modified natural cationic polymers are chitosan, cationic starch, polylysine and salts thereof.
  • the preferred synthetic cationic polymers include polymers obtained from homopolymerization of at least one cationic monomer (l b ) or copolymerization of l b with a copolymerizable monomer (II).
  • Suitable cationic monomers (l b ) include, but are not limited to, diallyldimethyl ammonium chloride (DADMAC), diallyldimethyl ammonium bromide, diallyldimethyl ammonium sulfate, diallyldimethyl ammonium phosphates, dimethallyldimethyl ammonium chloride, diethylallyl dimethyl ammonium chloride, diallyl di(beta-hydroxyethyl) ammonium chloride, and diallyl di(beta-ethoxyethyl) ammonium chloride, aminoalkyl acrylates such as dimethylaminoethyl acrylate, diethylaminoethyl acrylate, and 7-amin
  • the preferred cationic synthetic polyelectrolyte (B) are homopolymers or copolymers of diallyldimethyl ammonium chloride (DADMAC), diallyldimethyl ammonium bromide, diallyldimethyl ammonium sulfate, diallyldimethyl ammonium phosphates, dimethallyldimethyl ammonium chloride, diethylallyl dimethyl ammonium chloride, diallyl di(beta-hydroxyethyl) ammonium chloride, and diallyl di(beta-ethoxyethyl) ammonium chloride, aminoalkyl acrylates such as dimethylaminoethyl acrylate, diethylaminoethyl acrylate, and 7-amino-3,7-dimethyloctyl acrylate, and their salts including their alkyl and benzyl quaternized salts; ⁇ , ⁇ '-dimethylaminopropyl acryl
  • the preferred cationic natural polymers or modified natural polymers are chitosan, cationic starch, polylysine and salts thereof.
  • cationic polyelectrolyte(B) are preferably homopolymers or copolymers of diallyldimethyl ammonium chloride (DADMAC), diallyldimethyl ammonium bromide, diallyldimethyl ammonium sulfate, diallyldimethyl ammonium phosphates,
  • DADMAC diallyldimethyl ammonium chloride
  • bromide diallyldimethyl ammonium bromide
  • diallyldimethyl ammonium sulfate diallyldimethyl ammonium phosphates
  • the synthetic cationic polyelectrolyte (B) is a homopolymer or copolymer of DADMAC, dimethylaminoethyl acrylate or salts thereof including alkyl and benzyl quaternized salts.
  • the most preferred cationic polyelectrolytes for (B) are DADMAC homopolymers (pDAD), copolymers of DADMAC with diallylamine, chitosan, cationic starch, polylysine and salts thereof.
  • Suitable water-soluble cationic polymers are preferably reaction products of 0.1 to 100 weight percent, most preferably 10 to 100 weight percent, especially 50 to 100 weight percent, of at least one cationic monomer l b , preferably 0 to 90 weight percent, most preferably 0 to 50 weight percent, of one or more other copolymerizable monomers (II), and optionally, 0 to 10 weight percent of a crosslinking agent (III).
  • One particular embodiment makes use of PEMs featuring polyelectrolyte pairs (A) and (B) containing both strong and weak ionic groups in coatings for metallic medical devices and implants.
  • Strong anionic groups are preferably sulfate, sulfonate, phosphate, hydrogen phosphite, phosphoric acid, mixtures or salts thereof. Accordingly, a synthetic
  • polyelectrolyte (A) may be formed from monomers containing a sulfate, sulfonic acid, phosphate, hydrogen phosphite, phosphoric acid and phosphonic acid groups which when polymerized will give repeat units containing these moieties.
  • Weak groups are not fully charged but dissociate partially in solution depending on the pH of the solution or dispersion containing the polyelectrolyte (A) containing the weak anionic moieties.
  • the charge density of the weak anionic group is therefore pH dependent.
  • a weak anionic group will normally be more completely dissociated (ionized) at a high pH.
  • the weak anionic group will typically be a carboxylic acid.
  • the carboxylic group is located on the repeat units of polyelectrolyte (A) and the repeat units may be formed from monomers containing a carboxylic acid.
  • the number of weak anionic groups become deprotonated or negatively charged will increase with increasing pH.
  • a preferred embodiment is an polyelectrolyte (A) containing strong and weak anionic groups wherein the strong anionic groups are sulfate, sulfonic acid, phosphate, hydrogen phosphite, phosphoric acid and phosphonic acid groups and the weak groups are carboxylic acid groups.
  • synthetic polyelectrolyte (A) is a copolymer of styrene sulfonic acids, vinylsulfonic acid, allyl sulfonic acid, (meth)acrylamidopropyl sulfonic acid, vinyl phosphonic acid and salts thereof, especially styrene sulfonic acids and
  • Strong and weak cationic polyelectrolytes (B) are analogous to the strong and weak groups of the anionic polyelectrolytes (A) described above.
  • the strong cationic polyelectrolyte groups of (B) are permanent cationic groups independent of pH.
  • Strong cationic polyelectrolytes are preferably polymers containing quaternary ammonium, sulfonium, phosphonium groups, mixtures or salts thereof. Accordingly, a synthetic polyelectrolyte (B) may be formed from monomers containing a quaternary ammonium, sulfonium, phosphonium groups which when polymerized will give repeat units containing these moieties.
  • the B polyelectrolyte may be a natural polymer containing strong and cationically charged groups.
  • quaternized chitosan and cationic starch are well known in the art.
  • the term weak in reference to (B) means these groups are not fully charged but dissociate partially in solution depending on the pH of the solution or dispersion containing the polyelectrolyte (B).
  • the charge density of the weak base group is therefore pH dependent.
  • a weak cationic group will normally be more completely dissociated (ionized) at a low pH.
  • the weak cationic group will typically be a primary, secondary or tertiary amine.
  • the amine is located on the repeat unit of the polyelectrolyte (B) and the repeat units may be formed from monomers containing the primary, secondary, tertiary amine or acid addition salts thereof.
  • a weak cationic group can become positively charged when it associated with a positively charged proton H + and thus the pH will affect the amount of the protonated cationic weak groups.
  • the amount of cationic weak groups become protonated or positively charged will increase with decreasing pH.
  • the polyelectrolyte (B) is a synthetic copolymer of diallyldimethyl ammonium chloride (DADMAC), diallyldimethyl ammonium bromide, diallyldimethyl ammonium sulfate, diallyldimethyl ammonium phosphates, diethylallyl dimethyl ammonium chloride, diallyl di(beta-hydroxyethyl) ammonium chloride, and diallyl di(beta- ethoxyethyl) ammonium chloride, dimethallyldimethyl ammonium chloride,
  • DADMAC diallyldimethyl ammonium chloride
  • bromide diallyldimethyl ammonium bromide
  • diallyldimethyl ammonium sulfate diallyldimethyl ammonium phosphates
  • diethylallyl dimethyl ammonium chloride diallyl di(beta-hydroxyethyl) ammonium chloride
  • the invention further embodies the binder polymers containing hydrophilic entities in combination with an antimicrobial metal, preferably a metal salt to produce an improved corrosion resistant coating, especially on at least a part of a medical device and implant.,
  • the polymers binders binder comprising polymers selected from polyelectrolytes containing charged and/or potentially chargeable groups, preferably the polyelectrolyte is a complex derived from a positively-charged (cationic) polyelectrolyte and a negatively charged (anionic) polyelectrolyte and polymer containing hydrophilic entities, preferably the polymers containing hydrophilic entities forms a water-insoluble film.
  • water-insoluble polymers containing hydrophilic entities examples include copolymers of styrene and vinylpyridine, homopolymers and copolymers of vinylpyridine, homopolymers and copolymers of terbutylaminoethyl methacrylate.
  • the polymer binders containing hydrophilic entities include copolymers of styrene and vinylpyridine, homopolymers and copolymers of vinylpyridine, homopolymers and copolymer of terbutylaminoethylmethacrylate,
  • the polymer binders containing hydrophilic entities include a water-insoluble polymer coatings are made from block copolymers of vinylpyridine and styrene.
  • Coatings of the invention such as silver ion containing polyelectrolyte multilayer coatings, give excellent corrosion resistance to medical metals and alloys such as type 316L stainless steel.
  • the coatings improve corrosion resistance of medical metal substrates prolonging implant service time and reducing release of harmful substrate metal ions to the body and provide antimicrobial effect for infection control of medical implants.
  • Suitable antimicrobial metals, preferably salts or antimicrobial metal ions for the coating of the present invention to improve corrosion protection include ions from noble metals such as silver, copper, gold, iridium, palladium and platinum, for example, metal ions from silver and copper with known antimicrobial activity such as monovalent Ag(l) (or Ag + ) and divalent Ag(ll) (or Ag 2+ ), silver ions, both of which are known to be excellent antimicrobial and biocide agents.
  • Antimicrobial silver salts or silver ions are preferred.
  • Silver ions can be incorporated into the coatings by using inorganic and/or organic silver salts or complex silver ions.
  • Exemplary silver salt compounds include silver nitrate, silver sulfate, silver fluoride, silver acetate, silver permanganate, silver nitrite, silver bromate, silver salicylate, silver iodate, silver dichromate, silver chromate, silver carbonate, silver citrate, silver phosphate, silver chloride, silver bromide, silver iodide, silver cyanide, silver, silver sulfite, stearate, silver benzoate, and silver oxalate.
  • the above list of silver salts has reasonable water solubility and are well suited for use in solution for treating the polymer coating on the metal substrate.
  • complex silver ions examples include Ag(CN) 2 " , Ag(NH 3 ) 2 + , AgCI 2 " , Ag(OH) 2 " , Ag 2 (OH) 3 " , Ag 3 (OH) 4 " , and Ag(S 2 0 3 ) 2 3" .
  • the complex sliver ions can be prepared from a silver salt in an aqueous medium containing excessive amounts of a cationic or anionic or neutral species which are to be complexed with silver.
  • AgCI 2 " complex ions can be generated by placing AgN0 3 salt in an aqueous solution containing excessive amount of NaCI.
  • the Ag(NH 3 ) 2 + complex ions can be formed in aqueous solution by adding silver salt to excess ammonium hydroxide.
  • the Ag(S 2 0 3 ) 2 3" ions may be formed in aqueous solution by adding AgN0 3 to excess sodium thiosulfate.
  • the antimicrobial metal is preferably a salt which most preferably is a silver salt or complex of silver and is selected from the group consisting of silver nitrate, silver sulfate, silver fluoride, silver acetate, silver permanganate, silver nitrite, silver bromate, silver salicylate, silver iodate, silver dichromate, silver chromate, silver carbonate, silver citrate, silver phosphate, silver chloride, silver bromide, silver iodide, silver cyanide, silver, silver sulfite, stearate, silver benzoate, silver oxalate, Ag(CN) 2 " , Ag(NH 3 ) 2 + , AgCI 2 " , Ag(OH) 2 " , Ag 2 (OH) 3 -, Ag 3 (OH) 4 -, and Ag(S 2 0 3 ) 2 3 - .
  • a salt which most preferably is a silver salt or complex of silver and is selected from the group consisting of silver nitrate, silver
  • the coatings or the polymer binder of the invention may be applied to the metal substrates by any means known in the art e.g., brushing, spraying, drop casting, spin coating, draw down, substrate immersion etc.
  • immersion or dipping for a specific period of time is a simple and reproducible process providing excellent results and is an excellent approach for layer by layer deposition.
  • the polyelectrolytes (A) and (B) can be formed by a sequence wherein a substrate is conveniently immersed or dipped into a solution of a cationic polymer, removed, rinsed, and then immersed or dipped into a solution of an anionic polymer before being removed and rinsed. The sequence may be repeated until a film of the desired thickness is prepared. No drying is required between application of the polyelectrolyte (A) and (B).
  • Incorporation of the antimicrobial metal ions into the coating can be realized either by first applying the polymer binder on the substrate and then treating the applied binder with a solution containing the antimicrobial metal or antimicrobial metal ions can be incorporated into the polymer first followed by applying the antimicrobial metal ion containing polymer to the substrate.
  • the antimicrobial metal ion containing coating is achieved by using a polymer containing functional groups capable of complexing with antimicrobial ions in the coating composition; in another embodiment by coating the substrate with a polymer coating composition in which the antimicrobial salt is dissolved.
  • the silver can be incorporated in one of the
  • polyelectrolyte solutions used for PEM coating preparation and then applied to the metal.
  • One particular method for preparing a metal containing polymer of the invention involves bringing a metal compound or salt, e.g., a silver metal compound or silver metal salt in contact with an environment containing a polymer having capability of binding or complexing with silver.
  • a metal compound or salt e.g., a silver metal compound or silver metal salt
  • Polymers capable of complexing with silver include anionic polymers or anionic polyelectrolytes which contain anionic acid functional groups such as carboxylate, sulfate, sulfonate, phosphate, and phosphonate for electrostatic complexing with positive silver ions.
  • silver containing anionic polymers include but not limited to silver salts of poly(acrylic acid), and silver salts of copolymers of acrylic acid with copolymerizable monomers, poly(maleic acid) and copolymers of maleic acid, poly(styrenesulfonic acid) and copolymers of styrenesulfonic acid such as
  • Polymers containing metal chelating functional groups can also be used to prepare a metal containing polymer, e.g., a silver containing polymer.
  • the metal chelating functional groups include but not limited to (primary, secondary and tertiary) amino groups and ketocarboxylate such as acetoacetate groups.
  • Example of such polymers are (homo- and co-) polymers of vinylpyridine, vinylimidazole, diallylamines which cyclopolymerized to give pyrrolidine functional groups, allyamine, vinylamine (derivatives of vinylacetamine polymers), dimethylaminoethyl acrylate and 2- (acetoacetyl)ethyl methacrylate.
  • Polymers containing amino groups are potential cationic polymers or polyelectrolytes when being neutralized with an acid.
  • the coatings of the invention provide excellent anticorrosion activity even when applied as thin films, e.g., less than 10 microns for example less than 5, 2 or 1 micron thick and in certain embodiments less than 0.5 or 0.1 micron.
  • the coatings of the present invention are preferably from 0.05 to 15 microns thick.
  • the coating optionally comprises phytic acid and/or salts of phytic acid.
  • the application of phytic acid to the metal substrate can take place either as a pretreatment before coating with the binder polymer and antimicrobial,
  • the phytic acid may be also be applied in combination with the silver salt before application of the binder polymer.
  • the phytic acid is applied directly to the metal substrate surface before the polymer binder and antimicrobial metal is applied.
  • Film thickness, morphology and layer-by-layer film buildup is measured using AFM and ATR-FTIR. Electrochemical methods are used to evaluate corrosion of uncoated and coated samples.
  • the substrate to be tested for example a coated or uncoated metal wire, is placed in an electrochemical cell containing an electrolyte solution (0.7M NaCI in deionized water with a pH of about 6.0 or phosphate buffered saline (PBS) with a pH of 7.4), so that the area of the substrate immersed dipped in the electrolyte solution is 1.0 cm 2 .
  • the substrate is used as a working electrode in an electrochemical cell containing the electrolyte solution, a Ag/AgCI (3M NaCI) reference electrode and a platinum wire counter electrode.
  • the electrolyte solution in the cell is purged with high purity nitrogen before starting the testing.
  • the tests are carried out continuously in the sequence listed in Table B.
  • Open circuit potential (OCP) monitoring, anodic polarization scans and chronoamperometric scans were obtained using a SOLARTRON 1287A
  • Electrochemical Impedance Spectroscopy was carried out using a SOLARTRON 1252A FREQUENCY RESPONSE ANALYZER (FRA) with a ZPLOT software over the frequency (f) of 300,000 to 0.05 Hz with 5 mV AC amplitude.
  • the PD-1 measurement provides corrosion potential, E corr , corrosion current, l corr , and polarization resistance, R p , of free corrosion near OCP, pitting and breakdown corrosion potential, E b .
  • the PS-2 measurement tests long term durability of the coatings, i.e., 14 hours testing of static anodic polarization at pitting breakdown potential of bare type 316 stainless steel (700 mV). When pitting breakdown occurs during the PS-2 test, the time it begins (t b ) is reported.
  • the corrosion potential (E corr ) is slightly lower than, but close to, the open circuit potential (E oc ).
  • 0.05 Hz Z(0.05Hz) measured in Zplot-1 testing, is used to compare corrosion resistance of different samples. Similar to R p, a high Z(0.05Hz) value indicates high corrosion resistance.
  • LbL Layer-by-layer assembled polyelectrolyte multilayer films
  • the PEM coating has 20 double layers and ends with anionic polymer A as the outmost layer.
  • the PEM coating has 20.5 double layers and ends with cationic polymer B as the outmost layer.
  • Example 1 PEM2 coatings with 20 double layers of polymer A1 and Polymer B2
  • DIW deionized water
  • Polyelectrolyte multilayer coatings of 20 double layers of polymer A1 and polymer B2 (PEM2) 20 are deposited on the freshly abraded and ultrasonically cleaned 316LVM stainless steel wires following the above general layer-by-layer deposition method using a 10 mM poly(styrenesulfonate-co-maleic acid) sodium salt (A1 ) in 0.25M NaCI aqueous solution as the dipping solution for Polymer A solution and a 10 mM Poly(diallylamine-co-DADMAC) (B2) in 0.25M aqueous solution as the dipping solution for Polymer B.
  • A1 poly(styrenesulfonate-co-maleic acid) sodium salt
  • B2 10 mM Poly(diallylamine-co-DADMAC)
  • Incorporation of silver salt into the PEM2 coatings containing silver was accomplished by immersing the PEM2 coated SS316LVM wires in 0.25M silver nitrate aqueous solution overnight followed by rinsing with deionized water (DIW) and drying under a nitrogen stream. Uncoated SS316LVM wires were also treated in the same conditions for comparison in corrosion testing. Uncoated abraded and washed wires were also reserved as a control for testing.
  • DIW deionized water
  • Electrochemical corrosion tests were carried out on coated and uncoated SS316LVM wires in 0.7M NaCI solution.
  • the potentiodynamic polarization curves from the PD-1 testing are compared in Figure 1 for bare SS316L wire (B curve), SS316L wire coated with 20 double layer PEM-2 polymers (C curve), and SS316L wire coated with 20 double layers of PEM-2 polymers and treated with silver solution (A curve). Bare
  • SS316L wires show significant pitting corrosion with a breakdown potential E b of 700 mV, beyond which a sustained corrosion current occurs.
  • the plot for bare wire also contains random current spikes indicating meta-stable pitting before pitting breakdown at 700 mV.
  • Wires coated with 20 double layer of PEM-2 coatings exhibit significant improvement in corrosion resistance. The meta-stable pitting is suppressed and there is no pitting breakdown up to the 900 mV potential observed.
  • Treatment of the PEM-2 coated wires with AgN0 3 solution provides significantly further improvement in corrosion resistance.
  • the anodic polarization current for (PEM-2) 2 o+Ag coatings is significantly lower than that for (PEM-2) 2 o coatings only ( Figure 1 ).
  • the free corrosion properties near OCP are also improved significantly as shown by the data in Table 1.
  • the corrosion potential, E corr increased from 21 to 84 mV
  • corrosion current, l corr decreased about 5 times from about 30 to 6 nA/cm 2
  • the polarization resistance, R p increased more than 7 times from 714 to 5440 kQ * cm 2 .
  • the silver treated and bare SS316LVM wires are subjected to the same electrochemical corrosion tests.
  • SS316LVM treated only with silver solution gave little improvement in anti-corrosion properties.
  • the treatment of SS316L with the silver salt solution raised the corrosion potential, E corr but did not suppress pitting corrosion breakdown.
  • the silver treated wire had a pitting corrosion breakdown potential (610 mV) lower than that (700 mV) for untreated wire.
  • This example demonstrated synergy of the silver salt solution treatment with polyelectrolyte multilayer (PEM) coatings for anti-corrosion improvement on medical grade SS316LVM stainless steel. Significant improvement in anti-corrosion properties can be achieved by silver treatment of coated SS316LVM.
  • PEM polyelectrolyte multilayer
  • Figure 1 Potentiodynamic polarization curves from the PD-1 testing, bare SS316L wire (curve C), SS316L wire coated with 20 double layer PEM-2 polymers (curve B), and SS316L wire coated with 20 double layers of PEM-2 polymers and treated with silver solution (curve A)
  • Uncoated bare SS316LVM wires are abraded and washed as above and then immersed in 0.25M silver nitrate aqueous solution overnight.
  • the treated wires are rinsed with deionized water (DIW) and dried with a nitrogen stream and subjected to the same electrochemical corrosion tests as in Example 1.
  • DIW deionized water
  • wires treated only with silver solution gave little improvement in anti- corrosion properties.
  • the treatment of SS316L wire with the silver salt solution raised the corrosion potential, E corr but did not suppress pitting corrosion breakdown.
  • the silver treated wire had a pitting corrosion breakdown potential (610 mV) lower than that (700 mV) for untreated wire.
  • Table 2 Data from Zplot-1 , PD-1 and PS-2 tests for Ag treated and untreated SS316L wires.
  • Figure 2 Potentiodynamic polarization curves from the PD-1 testing, bare SS316L wire (curve C), SS316L wire treated with AgN0 3 solution (curve B)
  • Example 2 PEM2 coatings with 12 double layers of polymer A1 and Polymer B2 The procedure of Example 1 is repeated except that 12 instead of 20 double layers of polymer A1 and polymer B2 (PEM2) 12 , with and without silver salts, were deposited on the wires.
  • the PD-1 electrochemical corrosion testing results are shown in Figure 3 and Table 3.
  • the silver treated PEM2 coatings gave low corrosion current density (l corr ) and high corrosion potential (E corr ) and polarization resistance (R p ).
  • the benefit of improved anticorrosion properties from incorporating silver ions in the PEM2 coatings can also be seen with reduced double layers number (12) and thus decreased coating film thickness.
  • Figure 3 Potentiodynamic polarization curves from the PD-1 testing, bare SS316L wire (curve C), SS316L wire coated with 12 double layer PEM-2 polymers (curve B), and SS316L wire coated with 12 double layers of PEM-2 polymers and treated with silver solution (curve A)
  • Example 3 PEM2 coatings with 2 double layers of polymer A1 and Polymer B2 Polyelectrolyte multilayer coatings, with and without silver salts, comprising 2 instead of 20 double layers of polymer A1 and polymer B2 (PEM2) 12 were prepared on SS316LVM wires and tested as in Example 1 .
  • the PD-1 electrochemical corrosion testing results are shown in Figure 4 and Table 4.
  • the silver treated PEM2 coatings gave low corrosion current density (l corr ) and high corrosion potential (E corr ) and polarization resistance (R p ).
  • the benefit of improved anticorrosion properties from incorporating silver ions in the PEM2 coatings is realized with PEM coatings of only 2 double layers.
  • Figure 4 Potentiodynamic polarization curves from the PD-1 testing, bare SS316L wire (curve C), SS316L wire coated with 2 double layer PEM-2 polymers (curve B), and SS316L wire coated with 2 double layers of PEM-2 polymers and treated with silver solution (curve A)
  • DIW deionized water
  • 316LVM stainless steel wires were immersed in a solution of 10 mM of phytic acid and 0.25 NaCI for 40 minutes, rinsed with deionized water for 1 minute and dried with nitrogen stream flow.
  • Such phytic acid treated wires are identified by symbol Py for the phytic acid monolayer coating.
  • Phytic acid treated SS316LVM wires were immersed in a 0.25M silver nitrate aqueous solution overnight. The silver treated wires are rinsed with deionized water (DIW) and dried with a nitrogen stream and identified by symbol Py-Ag.
  • DIW deionized water
  • Electrochemical corrosion tests were carried out on coated and uncoated SS316LVM wires in 0.7M NaCI solution.
  • the potentiodynamic polarization curves from the PD-1 testing are compared in Figure 5 for bare SS316L wire (curve C), SS316L wire coated with monolayer of phytic acid (curve B), and SS316L wire coated with monolayer of phytic acid complexed with silver (curve A).
  • Bare SS316L wires show significant pitting corrosion with a breakdown potential E b of 700 mV, beyond which a sustained corrosion current occurs.
  • the plot for bare wire also contains random current spikes indicating meta-stable pitting before pitting breakdown at 700 mV.
  • the wires coated phytic acid monolayer exhibit improvement in corrosion resistance. No pitting breakdown up to the 900 mV potential is shown (E b > 900 mV) although the meta-stable pitting is still observed.
  • Treatment of Py coated wires with AgN0 3 solution provides significantly further improvement in corrosion resistance.
  • the anodic polarization current for Py+Ag coatings is significantly lower than that for Py coatings only and the meta- stable pitting is suppressed (Figure 5).
  • the free corrosion properties near OCP are improved significantly as shown by the data in Table 5.
  • the corrosion potential, E corr increased from negative ( ⁇ -128) to positive (> 30 mV)
  • corrosion current, ⁇ corri decreased about 5 times from about 25 to 5 nA/cm 2
  • the polarization resistance, R p increased more than 2 times from 670 to 1520 kQ * cm 2 .
  • Figure 5 potentiodynamic polarization curves from the PD-1 testing for bare SS316L wire (curve C), SS316L wire coated with monolayer of phytic acid (curve B), and SS316L wire coated with monolayer of phytic acid complexed with silver (curve A)
  • Example 5 PEM3 coatings with polymers A13 (Dextran sulfate) and B8 (chitosan) Freshly abraded and ultrasonically cleaned 316LVM stainless steel (SS316LVM) wires were immersed in a solution of 10 mM of phytic acid and 0.25 NaCI for 40 minutes, rinsed with deionized water for 1 minute and dried with nitrogen stream flow.
  • polymers A13 Disuln sulfate
  • B8 chitosan
  • Polyelectrolyte multilayer coatings of 20 double layers were prepared on phytic acid treated SS316LVM wires ((CTS/DXS) 2 o-Py) in the same ways as described in Example 1 except that dextran sulfate (DXS) was used for polymer A and chitosan (CTS) for polymer B.
  • DXS dextran sulfate
  • CTS chitosan
  • Some of the ((CTS/DXS) 2 o-Py coated wires were treated with AgN0 3 solution the same way as described in Example 1 to obtain silver treated PEM3 coatings ((CTS/DXS) 2 o-Py-Ag).
  • the PD-1 electrochemical corrosion testing results are shown in Figure 6 and Table 6.
  • Example 6 PEM1 coatings of polymers A2 and B7 on titanium alloy
  • Polyelectrolyte multilayer coatings of 20 double layers of polymer A2 and polymer B7 (PEM1 ) 20 are deposited on freshly abraded and ultrasonically cleaned titanium 6AI 4V (Ti6AI4V) wires using the above stated layer-by-layer deposition method.
  • the PEM1 coatings are obtained from Polymer A solution made of 10 mM
  • poly(styrenesulfonate) sodium salt (A2) in 0.25M NaCI aqueous solution and Polymer B solution made of 10 mM poly(diallyldimethylammonium chloride) (B7) in 0.25M aqueous solution.
  • PEM1 +Ag coatings containing silver are obtained by treating PEM1 coated Ti6AI4V wires in 0.25M silver nitrate aqueous solution overnight. The treated wires are rinsed with deionized water (DIW) and dried with a nitrogen stream.
  • DIW deionized water
  • Ti6AI4V wires in 0.7M NaCI solution The results are summarized in Table 7.
  • the potentiodynamic polarization curves from the PD-1 testing are compared in Figure 7 for bare Ti6AI4V wire (C curve), Ti6AI4V wire coated with 20 double layer PEM-1 polymers (B curve), and Ti6AI4V wire coated with 20 double layers of PEM-1 polymers and treated with silver solution (A curve).
  • Titanium alloys have the reputation of being high corrosion resistance. Indeed, the bare uncoated Ti6A4V wire did not show any pitting corrosion breakdown with applied anodic polarization up to 1 100 mV in the PD-1 corrosion testing ( Figure7).
  • the Ti6A4V wire coated with PEM-1 coating (220TW) improved the corrosion resistance in the low potential region ( ⁇ 500 mV) by significantly increasing the corrosion potential value (E corr ) from -250 mV to -25 mV and reducing corrosion current density at the same applied potential.
  • FIG. 7 Potentiodynamic polarization curves from the PD-1 testing for bare Ti6AI4V wire (curve C), Ti6AI4V wire coated with 20 double layer PEM-1 polymers (curve B), and Ti6AI4V wire coated with 20 double layers of PEM-1 polymers and treated with silver solution (curve A).
  • Example 7 Single polymer (PSt-b-P2VP) coatings on SS316LVM
  • Vacuum arc remelted stainless steel 316LVM (ASTM F138 chemistry) wires (1.25 mm in diameter were abraded with SiC (1200 grit) sand paper, degreased with isopropanol, and then washed with deionized water (DIW) in an ultrasonic bath for 10 minutes. Some of such cleaned wires were tested as is uncoated and served as a control for comparison.
  • Block copolymer of polystyrene and polyvinylpyridine (PSt-b-P2VP) was prepared by anionic polymerization .
  • the PSt-b-P2VP block copolymer used in this example has a PS/P2VP composition ratio of 1.0 and a weight average molecular weight (Mw) of about 65,000 with a polydispersidy of 1.31 as determined by GPC using narrow molecular weight polystyrene standards.
  • PSt-b-P2VP polymer coatings were prepared on freshly cleaned SS316L wires by dipping two times in a 2.5% by weight of the PSt-b-P2VP polymer solution in PGMEA (propylene glycol monomethyl ether acetate) and air dried.
  • PGMEA propylene glycol monomethyl ether acetate
  • PSt-b-P2VP+Ag coatings containing silver are obtained by treating PSt-b-P2VP coated SS316LVM wires in 0.25M silver nitrate aqueous solution for four hours. The treated wires are rinsed with deionized water (DIW) and dried with a nitrogen stream.
  • DIW deionized water
  • Electrochemical corrosion tests were carried out on coated and uncoated SS316LVM wires in 0.7M NaCI solution. Results are summarized and in Table 8.
  • the potentiodynamic polarization curves from the PD-1 testing are compared in Figure 8 for bare SS316L wire (black curve), SS316L wire coated with PSt-b-P2VP only (red curve), and SS316L wire coated with PSt-b-P2VP and treated with silver solution (blue curve). Bare SS316L wires show significant pitting corrosion with a breakdown potential E b of 700 mV, beyond which a sustained corrosion current occurs.
  • the plot for bare wire also contains random current spikes indicating meta-stable pitting before pitting breakdown at 700 mV.
  • the wires coated with only PSt-b-P2VP improved free corrosion resistance at low anodic potential but deteriorated pitting corrosion breakdown resistance.
  • the free corrosion potential E corr is increased, corrosion current l corr reduced, and the meta-stable pitting suppressed with PSt-b-P2VP coating.
  • the pitting breakdown still occurs and is reduced to 600 mV potential.
  • Treatment of the PSt-b-P2VP coated wires with AgN0 3 solution provides significantly improvement in corrosion resistance.
  • the anodic polarization current for PSt-b-P2VP+Ag coatings is significantly lower than that for PSt-b-P2VP coating only (Figure 8).
  • the free corrosion properties near OCP are improved significantly as shown by the data in Table 8. With silver solution treatment on the PSt-b-P2VP coated
  • the corrosion potential, E corr increased from -66 to 228 mV
  • corrosion current, l corr decreased about 4 times from about 4 to 1 nA/cm 2
  • the polarization resistance, R p increased more than 3 times from 2530 to 9860 kQ * cm 2 .
  • the incorporation of silver in PSt-b-P2VP polymer coatings suppressed pitting breakdown and could withstand long term corrosion test of PS-2 at 700 mV anodic polarization for more than 14 hours.
  • Figure 8 potentiodynamic polarization curves from the PD-1 testing for bare SS316L wire (curve C), SS316L wire coated with PSt-b-P2VP only (curve B), and SS316L wire coated with PSt-b-P2VP and treated with silver solution (curve A).
  • Example 8 silver ion incorporation and release for antimicrobial applications
  • pDADDAA PSSMA Twenty double layers of pDADDAA PSSMA (PEM-2) were coated on 5x5 cm square type 316 stainless steel coupons with (16zs200PC) and without (16zs200DC) phytic acid pre-treatment.
  • the PEM-2 coated coupons were immersed in 0.25M AgN0 3 solution overnight to load silver ions and rinsed with deionized water and dried by nitrogen blow at room temperature.
  • the thus silver loaded coupons were immersed in 30 g of deionized water for releasing silver ions.
  • the coupons were removed from the Ag+ released water and placed into 30 g of fresh water for another cycle of Ag+ releasing.
  • the concentration of silver ions in the Ag+ released water was determined using a Ag/AgS silver ion selective electrode (Ag ISE).
  • the results are shown in Figure 9.
  • the total amount of silver ions loaded to the PEM coatings can be estimated from the releasing experiments to be about 6.0 and 7.8 ⁇ g cm 2 for 16zs200DC and 16zs200PC, respectively. It appeared that phytic acid (16zs200PC) can improve the Ag+ ion loading capacity.
  • the silver loaded PEM-2 coatings on the SS316 coupons with 50 cm 2 surface area can maintain about 0.7 ppm of silver ion in 30 g of water after the second water change.
  • the Ag+ concentration decreased with each fresh water change but still above 0.1 ppm after the 5th water change.

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Abstract

L'intégration de métaux antimicrobiens, tels que des sels d'argent, dans un revêtement anticorrosion confère une excellente protection antimicrobienne et améliore aussi de façon étonnante l'activité anticorrosion, ce qui permet de former des revêtements anticorrosion efficaces comme films minces qui conviennent pour l'enrobage de dispositifs médicaux. Les polymères de liaison appropriés pour un tel revêtement comprennent notamment, mais pas exclusivement, des polyélectrolytes contenant des groupes chargés et/ou pouvant potentiellement être chargés et des polymères contenant des entités hydrophiles.
PCT/US2011/028503 2010-03-30 2011-03-15 Revêtement anticorrosion contenant de l'argent pour une protection accrue contre la corrosion et l'activité microbienne WO2011126684A2 (fr)

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US20110244256A1 (en) 2011-10-06
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